Production of drying oils



Dec. 16', 1952 H. s. BLOCH ETAL PRODUCTION oF DRYING oILs Filed May 29, 1948 /fzzz 0119: ervzzajz 5320612 Patented Dec. 16, 195,2

PRODUCTION OF DRYING OILS Herman S. Bloch, Chicago, and Richard C. Wackher, La Grange, Ill., assignors to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware Application May 29, 1948, Serial No. 30,157

(Cl. i560-666) Claims.

This invention relates to a process for producing drying oils by converting mixtures of carbonylic compounds and olefmic hydrocarbons having at least 3 carbon atoms per molecule. More particularly, the invention is concerned with the production of a substantially saturated liquid hydrocarbon product and a higher boiling unsaturated liquid product by polymerization and hydrogen transfer reactions of a carbonylic compound and an olenic hydrocarbon having at least 3 carbon atoms per molecule.

One of the objects of this invention is the manufacture of an unsaturated liquid product having more than one double bond per molecule.

A further object of this invention is the producton of a, substantially paraffinic hydrocarbon product and of a higher boiling unsaturated liquid organic material useful as a drying oil.

One specific embodiment of this invention relates to a process for producing a drying oil which comprises reacting a carbonylic compound and an olefinic hydrocarbon having at least 3 carbon atoms per molecule in the presence of a conjunct polymerization catalyst until a reaction mixture comprising substantially saturated hydrocarbons and polyunsaturated organic compounds is formed, separating the reaction mixture into a hydrocarbon layer and a catalyst layer, separating substantially saturated hydrocarbons from the hydrocarbon layer, and recovering from the catalyst layer a drying oil having an average molecular Weight greater than that of the olenic charge stock.

Another embodiment of this invention relates to a process for producing a drying oil which comprises reacting a carbonylic compound and an olenic hydrocarbon having at least 3 carbon atoms per molecule in the presence of a catalyst comprising a major proportion by Weight of hydrogen iiuoride until a reaction mixture comprising substantially saturated hydrocarbons and polyunsaturated organic compounds is formed, separating the reaction mixture into a hydrocarbon layer and a hydrouoric acid layer containing polyunsaturated organic compounds, separating substantially saturated hydrocarbons from the hydrocarbon layer, and recovering from the hydrofluoric acid layer a drying oil having an average molecular Weight greater than that of the olefinic charge stock.

A further embodiment of this invention relates to a process for producing a drying oil which comprises reacting a carbonylic compound and an oleiinic hydrocarbon having at least 3 carbon atoms permolecule in the presence of a catalyst mixture into an acid phase and a hydrocarbon phase, separating substantially saturated hydrocarbon products from the hydrocarbon phase, and recovering from the acid phase a drying oil having an average molecular weight greater'than that of the oleiinic charge stock.

In still another embodiment of this invention,k a carbonylic compound and a normally liquid monoolen hydrocarbon are subjected to polymerization and hydrogen transfer reactions in the presence of a catalyst consisting essentially of hydrouoric acid containng less than about 10% by Weight of Water at a reaction temperature and for a time suiiicient to effect formation of a saturated hydrocarbon layer and a heavier lower layer comprising essentially hydrogen iiuoride and a highly unsaturated organic material, the reaction mixture is separated into a hydrogen fluoride catalyst layer and a hydrocarbon layer, substantially saturated hydrocarbon products having more carbon atoms per molecule than the charged liquid monooleiln are separated from the hydrocarbon layer, and an unsaturated drying oil is recovered from the hydrogen iiuoride layer.

Monoolenic hydrocarbons utilizable in the process have at least 3 carbon atoms per molecule and comprise propylene, the butylenes, pentenes,

may also contain certain amounts of parainic and naphthenic hydrocarbons some of Which may be alkylated during the polymerization treatment. C3 and C4 fractions recovered from the products of cracking and a C4 fraction recovered from butane dehydrogenation and containing mainly butylenes and normal butane with relatively little isobutane are also good charging stocks for this process.

This invention relates to the conjunct co-polymerization of aliphatic olefinic hydrocarbons with certain polar compounds characterized by possession of one or more groups of the type and otherwise lacking in unsaturation. Such compounds are capable of enolization, and although it is doubtful whether they actually enolize under the conditions of conjunct polymerization, they appear to undergo conjunct copolymerization with the hydrocarbon olens to form apolyenic product containing oxygen. Examples of such materials containing carbonyl groups are diacetone alcohol, triacetin, ethyl laurate, polyvinylacetate, the ethylene glycol ester of adipic acid, the polyamide of hexamethylene diamine and adipic acid, acetophenone, cyclopentanone, acetoacetic ester, diethylmalonate, phenylacetic acid, heptaldehyde, butyric Yacid amide,' and the like; or, in general, saturated compounds containing aldehyde, ketone, carboxylic acid, ester, or amide groups. The carbonylic compounds used in this process may also contain carboxylic acid groups such as are present in pyruvic acid (CHaCOCOOH), in levulinic acid (CHsCOCHzCHzCOOH), and in other polyfunctional compounds.

Hydrogen fluoride catalysts employed in the present process and also referred to as hydrofluoric acid catalysts contain a major proportion by Weight of hydrogen fluoride and generally at least 90% by weight of hydrogen fluoride and as much as by Weight of Water, although the titratable acidity of the catalyst layer may be less than 90% because of the presence therein of dissolved organic compounds including highly unsaturated'polymer which is hereinafter described more completely. The preferred catalyst for this process is substantially anhydrous hydrogen fluoride, that is, 100% HF, or the commercial grade thereof, which contains 98+ HF.

Other conjunct polymerization catalysts utilizable in the production of drying oils from a sludge containing the same and produced under reaction conditions similar to those employed for the formation of a sludge from a hydrogen uoride catalyst, include in general, certain acidacting halides such as aluminum bromide and aluminum chloride, in their substantially anhydrous forms, sulfuric acid of at least about 85% concentration, boron triuoride and mixtures of boron trifluoride and hydrogen iiuoride. These other Vcatalysts `form conjunct polymerization products which are structurally and physically similar to the conjunct polymers formed when hydrogen fluoride is utilized as the catalyst herein, but differ chieiiy in the manner of recovering the conjunct polymers from sludges containing said catalysts. Because hydrogen fluoride sludges may be decomposed under such conditions that the catalyst may be recovered in a substantially anhydrous condition, suitable for recycling to the sludge-forming stage, it is generally preferred in the present process. Y

The operating temperature employed in this process has a profound influence upon the nature of the reaction occurring when a carbonylic compound andan olenic hydrocarbon are contacted with a-conjunct polymerization catalyst, for example, with hydroiiuoric acid of 90 to 100% concentration.Y Partof this effect of temperature may be dueto the behavior of the olens themselves in the presence of hydrogen fluoride- '4 Ethylene reacts with hydrogen iiuoride to form ethyl fluoride and also certain amounts of polymers at temperatures from about 0 to about 175 C. Propylene also gives some isopropyl uoride at the lower operating temperatures but conjunct polymer formation from propylene increases at the higher temperatures of treatment within the mentioned range of 0 to about 175 C.

In contrast with the behavior of ethylene which produces ethyl uoride as the chief product, the monoolens having at least 3 carbon atoms per molecule undergo extensive polymerization and condensation with carbonylic compounds particularly aldehydes and ketones in the presence of hydrogen uoride with only a small amount of alkyl fluoride formation at temperatures of from about 0 to about 175 C. and preferably at temperatures of from about 10o to about 125 C. Also the vcondensation and polymerization of these olens and carbonylic compounds involves more than the simple combination of lolefnic molecules to form dimers, trimers, tetramers, and higher polymers. Y

It has been observed and these observationsY have been made the basis of the present process that when a mixture of olefinic hydrocarbons and carbonyl compounds is subjected to conjunct copolymerization in the presence of a conjunct polymerization catalyst heretofore specified, conjunct polymer product is formed in significantly film of excellent adherence which dries completely to a non-tacky, non-brittle film possess-v ing the desired properties of such lms for drying oil purposes. Further, the presence of carbonyl compounds such as diacetone alcohol, in the charging stock tends to increase the yeld of conjunct polymers obtained from a given weight of charge and conjunct polymerization catalyst. The latter effect is believed to be due to the increased number of hydrogen acceptors per unit weight of reactants charged to the process.

The complex series of reactions herein referred toV in the aggregate as a conjunct polymerization reaction comprises an initial polymerization and condensation reaction between the olenic and carbonylic components of the charging stock and as the reaction progresses further, cyclization and isomerization of the polymers and condensation products occur, accompanied by a hydrogen transfer reaction between the organic compounds or conjunct polymers present in the reaction mixture whereby a portion of the conjunct polymers are converted into saturated hydrocarbons by virtue of the hydrogen transfer at the expense of other components which are converted into hightly unsaturated organic compounds containing on :an average of from about 2.5 to about 4 double bonds per molecule of Which from about to about 70% are conjugated. The resulting unsaturated conjunct polymers comprising a series of high molecular Weight polyolenic cyclic compounds become attached by weak chemical bonds to the catalyst to form a sludge-like complex addition product in which the iuorine (in the case of a hydrogen fluoride catalyst) is not, however, organically bound, since it can be substantially all recovered by treatment of the complex with water or aqueous alkali. The

lsaturated. hydrocarbon conjunct polymers form amamos aninsoluble phase which yupon settling Aofc-therelaction mixture separates as adistinct uppenlayer hereinabove referred to. Since the formation; of the unsaturated conjunct. polymeris dependent upon the presence of. hydrogen. acceptors' in the reaction mixture,.it also followsthat.the-proportion ofhydrogen acceptorsto hydrogendonors influences the total .unsaturationof thepolyolenic conjunct. polymers formed,v as well as their yield; from givenweights of hydrocarbons. and carbonyl compounds charged. The knowledge of the relationship. between unsaturationv ofthe-.hydrocarboncharginglstock and the unsaturation of the ultimate hydrocarbon dryingv oilproduct is embodied. in the utilization ofv an. admixture. of carbonyl compounds and monoolensas" charging stock.r inthe present process. to obtainfconjunct cci-polymerization. therebetween. and: to' form a rgreater yield of oonjunct` polymers having, somewhat diferent chemical structure than a product similarly prepared by conjunctpolymerization of a monoolefin only. Thek oxygen-modied structures ofthe yconjunct polymerslobtained in accordance with the process herein" provided are believedto be theA basic factorsinvolved inthe formation of the more adherent, more. elastic, and tougher lm, on oxidation of the-drying. oil when exposed to atmospheric oxygen.

Study of the ultra-violet and infra-red absorption spectra and other propertiesA of drying oil fractions. formed from vpolymer gasoline andiboiling from about 150'to about 200 C., shows that many of these drying oil hydrocarbons'contain a pair of conjugated double bondswith one of these double bonds ina ring of 5 carbon atoms and the other double bond in an alkenylside chain. Thus a cyclopentene ring may be combined with a methylene group/or a vinyl group. However, some of the drying oil hydrocarbons may also contain a cyclopentadiene ring. The drying oil hydro- -z carbons which contain a cyclopentenyl ring'also contain morev than twoy substituent groupsA but cach of these groups is highly'substituted". The highelI boiling fractions of this drying oil boiling up to about 450C. contain polycyclic hydrocarbons which are generally bicyclic. In both the monocyclic and polycyclic hydrocarbons the vecarbon atom` ring portions of the molecules are combined with at leastl two alkyl groups or two wherein the radicals Rlvto R10 are selected from the group consisting ofv hydrogen and alkyl, alkenyl and alkapolyenyl hydrocarbon radicals, at least two of thexsubstituentsR* to R10 are hy'- drocarbon radicals,y and. not more i than. .two f ofthe groups R1 tofR* representhydrcgen.

Alkapolyenyl y wherein R1 toR8 represent members of the group consisting of. hydrogen and. alkyl, allienyl,` and alkapolyenyl hydrocarbon radicals, at least two of the substituents R3 tov 1i.a are hydrocarbon radicals,and.. not more than two ofV the substituentsRl to R4 :are hydrogen.

The. drying. oils ofthe present process contain organic compoundshav-ing some ofv the; aforementioned flve-carbon :atom ring structurescondensed with a carbonylic compound.

The condensation productswhich are formed from. the olenic hydrocarbons and carbonyl compounds are of higher molecular weight than the olefinic hydrocarbon charging stock and have goo-d drying oil properties. Such drying oils which mayv Ibe regarded as mixturesof condensation products, and high boiling conjunct polymers havel a high degree of conjugated and nonconjugated unsaturation. These drying oils have the advantagey that they form protective lms that are less brittle, more adherent, and more dura-ble than those formed from high boiling unsaturated. oils. produced similarly from monoolen hydrocarbons without the addition of car- 'bony-lic. compounds.

'Ihis condensation or co-polymerization process for producing drying. oils may -be modied 'further by incorporatinginthe reaction mixture a certain` amount of amore unsaturated olenic hydrocarbon, namely,.a dienic hydrocarbon such as, for example, butadiene-1,3, isoprene, cyclopentadiene,` and the; like; orA an acetylenic hydrocarbon.

Theprocessconsists-essentially of contacting a mixture of an olenic hydrocarbon and a carbonylic compound with substantially anhydrous hydrogen uoride at coniunct polymerization conditions, separating the upper saturated hydrocanbon, layer from the lower catalyst sludge layerand.then decomposing. the sludge by water hydrolysis, by heating, or by otherv suitable -means to recover the drying. oil therefrom. Improvement in adhesive properties, of the drying` oil product isobservedwhen-about 2. mole per cent of thev carbonyl compound isv present. When more than about an equal molecular proportion of carbonyl compoundis present, the vvamount of condensation and speed of the condensation proces-s are retarded. Accordingly, the molar ratio of olento carbonylic compound will` depend upon the properties desired in the, product but. may vary fromv about 1 vto about 50. The weight ratio of hydrogen fluoride. catalyst to organic charging stock, that is, thecombined mixture of carbonylic compounds and. olei'lnicv hydrocarbon, may vvaryfrom about 0.1 to about 10. When the hydrogenuoride to organic compound weight ratio is less thanv yabout 0.1, 'it is necessary tof recycle excessive amounts of organic compoundsin order to 'obtain good conversion while increases-'in'. this'ratio above about 10 effect very littlefurther. increase in yieldof the desired reaction products .but such; increased ratio of hydrogen uoride to` organic reactants does decrease the more unsaturated than the charge stock.

capacity of the' reaction and other treating equipment. Y

The present process is carried out at a temperature 'of from labout 0 to about 175 C. and at a pressure sufficient to maintain the reactants and catalyst in substantially liquid phase. The operating pressure is generally from about 1 to about 100 atmospheres. At these reaction conditions, la vigorously agitated mixture of hydrogen iiuoride, carbonylic compound and yolenic hydrocarbon containing at least 3 carbon atoms per molecule yields a high proportion of catalyst layer containing polyunsaturated organic compounds dur-ing a time of from about 1 to yabout 30 minutes, but the reaction may be continued for a longer time to obtain a better yield of the polyunsaturated organic compounds and a more highly saturated hydrocarbon mixture which is separated as an upper layer from the hydrogen fluoride layer.

Oleiinic hydrocarbons having more than 3 carbon atoms per molecule are more desirable as charging stocks than propylene because of the increased yields of both saturated yand unsaturated liquid products and improved properties of the products obtained from these ypreferred charging stocks. About the same quantity and quality of -drying oil are obtained when charging any of the olens having from 4 to yabout 12 carbon yatoms per molecule. The different monoolens having at least 4 carbon atoms per molecule appear to be mutually interconverti-b-le by polymerization and depolymerization reactions at the conditions specified for this purpose.

It is of particular interest to note that in this type of co-polymerization, in which hydrogen transfer occurs, the product recovered from the sludge or catalyst layer has a higher molecular weight than the charge stock, and is generall It should be noted further that the introduction of polar groups into the polyenic -conjunct 'polymer permits further modification of this product. For example, if an alcohol group is introduced into the molecule by conjunctv polymerization, the product may be esteried subsequently with either monobasic or polybasic acids (which may, in turn, be saturated or unsaturated) to make a large variety of esters and polyesters having' a wide range of properties, or if acidic groups are introduced into the molecule by conjunct polymerization, the product may 'be esteried subsequently with either monohydric or lpolyhydric alcohols, or be reacted with amines, of either saturated or unsaturated type, to make a large variety of esters and amides having a wide range of properties.

In carrying out this process, a carbonylic compound, an olefinic hydrocarbon having at least 3 carbon atoms per molecule, and liquid hydrogen iiuoride are added to a reactor provided with adequate means for agitating the reactor contents and for controlling the temperature therein. Since the polymerization and co-polymerization reactions of this process are exothermic, it is generally necessary to cool the reactor in order to maintain a chosen reaction temperature. The carbonylic compound, olefin hydrocarbon, and hydrogen fluoride catalyst are generally mixed at such rates that substantially complete conversion of al1 of the organic compounds charged is eifected. After the desired quantity of organic material, comprising essentially olenic hydrocarbons and carbonylic compounds, has been added tothe hydrofluoric acid, orafter the hydroiiuoric acid has been added to the organic material, the agitation or stirring of the reaction mixture is generally continued for a time sucient to ensure substantially complete conversion of the reactants into saturated hydrocarbons and also `highly unsaturated organic liquids having drying oil properties. The agitation or mixing is then stopped and the reaction mixture is permitted to stand whereby it forms two layers: an upper substantially saturated hydrocarbon layer and a lower hydrogen uoride layer. The substantially saturated hydrocarbon layer is separated from the lower hydrogen iiuoride layer comprising essentially hydrogen fluoride and highly unsaturated organic material with drying oil properties.

' As the saturated hydrocarbons of the upper layer boil over about the same range of temperature as do the unsaturated drying oil constituents recoverable from the hydrogen fluoride lower layer and as small amounts of the saturated hydrocarbons are entrained or mixed with the hydrogen fluoride lower layer, it is advisable to extract the hydrogen iiuoride lower layer with a lowboiling saturated hydrocarbon, preferably a parain having from 3 to about 8 carbon atoms per molecule, before hydrolyzing, or otherwise decomposing, the hydrogen iluoride lower layer to recover the unsaturated drying oil therefrom. From the lower layer, the hydrogen fluoride and drying oil fractions areV then separated by suitable means, for example, the lower layer may be added to water or ice whereby the hydrogen uoride is dissolved in water to form an aqueous solution from which the drying oil separates as an upper layer. Also the lower layer may be subjected to flash distillation to vaporize the hydrogen iluoride from the higher boiling highly unsaturated drying oil. When the lower layer is separated by distillation methods, the recovered hydrogen uoride is suitable for recycling to the process to effect reaction of additional quantities of the charged monoolenic hydrocarbon -and carbonylic compound.

The passage of inert gas, such as nitrogen, hydrogen, methane, ethane, carbon dioxide, and the like through the distillation system in which the hydrogen fluoride is being separated, assists in the recovery of the highly unsaturated drying oil. Separation of hydrogen iiuoride from the drying oil present in the lower layer is also assisted by carrying out the distillation of said lower layer in a tower ycontaining catalytic packing material formed from graphitized carbon or from a metal selected from the members of the group consisting of aluminum, copper, cobalt, lead, cadmium, and an alloy of copper, such as brass, and preferably in the presence of an inert carrier gas to assist in removing the liberated hydrogen fluoride.

Another method of decomposing the hydrogen iiuoride-drying oil mixture of the lower layer formed by the reaction of hydrogen fluoride with a mixture of olens and carbonylic compounds, is to introduce the lower layer or sludge into an inert liquid such as a parainic hydrocarbon, contained in a decomposition zone and maintained at a temperature near its boiling point. The decomposition zone or Vreactor tower may contain a catalytic packing 'material in the liquid zone of this reactor tower and an inert gas may also be passed therethrough. Hydrogen iuoride so liberated is vaporized, condensed, and conducted to storage while the inert liquid containing the dissolvedhighly unsaturated drym" g oil,

aceaios iswithdrawn from the decomposition zone, either intermittently or continuously, and replaced by fresh liquid. This liquid should be readilyseparable from the drying oil dissolved therein and it should also be relatively inert to the hydrogen iiuoride sludge and to the products of the decomposition of the sludge. If a paraflinic naphtha is employed, its normal boiling point should be from about 100 to about 150 C. so that it maybe separated by vfractional distillation from the drying oil Which boils generally from about 150 to about '450 C.

One method yof carrying out the process of this invention 'is illustrated diagrammatical'ly by Figure 1 which is a flow diagram indicating the various steps of the process. According to the method illustrated, an olen-containing feed stock, such as a `butane-butylene or pentane-pentene mixture, is directed-through line `I to mixing zone 2 to whicha carbonylic compound such as dia'cetone alcohol is directed through line 3 and hydrofluoric acid of 90 to 100% hydrogen fluoride concentration yis introduced through line 4. Mixing Zone 2 comprises a coil, an agitated reaction Zone, or other mixing equipment, preferably provided with suitable temperature control means, such as, for example, a cooling or heating jacket or a cooling or heating coil in order to maintain the reaction mixture at a chosen temperature within the'limits of from about '0 to about 175 C. The reaction mixture present in mixing zone 2 may also contain recovered hydrogen fluoride and a low boiling .saturated-hydrocarbon which are separated from Athe final reaction products and recycled through lines .I2-and I5 respectively -to lines 4 and I hereinafter described. The olencontaining feed stock, carbonylic compound and hydrogen fluoride are contacted in mixing zone 2 for a time sufficient to convert substantially all'the olefin monomer and carbonylic compound into polymers and condensation products, and also to effect a `hydrogen transfer reaction vbetween the various polymers and condensation products so as to produce la substantially saturated hydrocarbon 4product-rand a highly unsaturated product, thev latter being associated with the liquid hydrogen fluoride catalyst. From mixing Yzone 2, the resultant .mixture is directed through line 5 to settling zone 6 wherein the mixture or emulsion of organic compounds and liquid hydrofluoric vacid is permitted to stand and Yto separate .into an upper hydrocarbon layer and a lower hydrofluoricacid catalyst layer. From settlingzone 6, the hydroiiuoric acid-catalyst layer is withdrawn through line i'to catalyst layer separating zone 8 while a substantially saturated hydrocarbon material whichseparates as an upper layer in zone 6 is directed therefrom through line 9 to hydrocarbon layer separating zone I0.

The hydrogen vfluoride catalyst' layer-in -sepalrating lzone!! is subjected 'to flash distillation to separate hydrogen fluoride from highly unsaturated organic material, comprising 4drying oil materials. The used hydrogenfflucride so separated in zone 8 lis directed therefrom through .line II and at least :a portion thereof is directed through recycle line I2 to line 4, and thence -to mixing -zone 2 already mentioned, while the highly unsaturated liquid drying oil material :is :discharged from vseparating zone A8 through line I3 to storage or to further purification `or fractionationnot illustrated in Figure 1.

The hydrocarbon layer so separated from used hydrogen fluoride catalyst in settling .zone 16 is subjected 'to suitable Yfractionation lin hydrocarbon separating yzone l0. Fractional distillation of the hydrocarbonaceous material present in zone I0 separates therefrom as an overhead fraction, a mixture of `residual dissolved hydrogen fluoride and substantially saturated low boiling hydrocarbons introduced to the process in the olefin-containing charging stock. Thus when charging a butane-butylene fraction, the hydrocarbon stream being directed from Aseparating zone I0 through line vIll is mainly normal butane while this stream is mainly normal pentane when a pentane-pentene mixture is charged to mixing zoner 2. If desired, va portion of the loW .boiling saturated hydrocarbon fraction which is discharged through line I4 may be directed therefrom through recycle 'line I5 to line I already mentioned through which the olefin-containing feed stock is directed to the process. After the removal of the low boiling saturated 'hydrocarbons in hydrocarbon separating zone I0, a vsubstantially saturated hydrocarbon product formed by the condensation, polymerization, and hydrogen transfer reactions is directed from zone I0 through line I6 to storage cr lto use -not -illustrated in the diagrammatic drawing.

When the oleiinic charging stock does not contain a substantial proportion of saturated hydrocarbons having from 3 to about 8 carbon atoms per molecule, it is Vadvisable to extract the hydroiiuoric acid layer with such a solvent before separating the drying oil ,from Ythe hydrofluoric acid `layer in separating zone 8.

The following examples ,are given to ,illustrate the process of this invention although the data introduced should not be misconstrued to limit unduly the broad scope of the invention.

EXAMPLE I Polymer gasoline and diacetone alcohol Were treated with hydrogen fluoride Yto produce adrying oil. The polymer gasoline, which boiled between 28 and 225 C. had a specific gravity, 1420, of 0.712, a Reid vapor pressure of 12.7 pounds per square inch, a bromine number of 132, a molecular Weight of and a sulfur content rof 0.04% by weight. In carrying out this process, grams of polymer .gasolineand .26 grams Yof diacetone alcohol were charged to a turbomixer autoclave of 1,000 cc. capacity, -the free space was iiushed With nitrogen and then 196 grams of anhydrous hydrogen fluoride was added to the mixture of polymer and diacetone alcohol. The resultant reaction mixture was stirred for one hour at a temperature of 90-95 C. and at a maximum pressureof 132 pounds .persquare inch. The resultant reaction mixture was then permitted to stand in a settler at L1 10". C. and separated into104 grams of an upper layer and 299 grams of a lower hydrofluoric Aacid layer. The upper layer after washing with Water, sodium bicarbonate solution, and again with Water, weighed 99.5 grams. The lower hydroiiuoric acid layer was hydrolyzed with water, and then washed with water to remove hydrogen fluoride. The Iorganic liquid obtained from the hydrolysis weighed 91 grams.

In this treatment 0f Va mixture of polymer gasoline and diacetone alcohol with anhydrous hydrogen fluoride, a typical conjunct polymerization occurred in which a saturated hydrocarbon layer and a lower hydrofluoric acid layer containing highly unsaturated compounds was obtained. Carbon and hydrogen analysis of the organic liquid obtained by hydrolyzing the hydrouoric acid layer showed the presence .of labout 1.8% oxygen which represents 23% of the oxygencharged in the diacetone alcohol. The 23% represents only a minimum Value of the percentage of the charged diacetone alcohol appearing in the lower layer product, since some of the oxygen may have been lost in dehydration reactions. The larger yield of unsaturated product, namely 91 grams, over a normal yield of '70 grams of drying oil product obtained from polymer gasoline alone shows that more than 23% of the diacetone alcohol appeared t undergo conversion.

Drying tests on the resultant drying oil recovered from the hydrogen fluoride layer and having a molecular weight of 254, showed that it dried hard in 2 to 3 days either in the presence or absence of driers such as naphthenates of cobalt, manganese and lead. The dried iilm of the drying oil had -a maximum Sward hardness of 16.

Other properties of the upper layer and lower layer hydrocarbons obtained by this reaction of polymer gasoline with diacetone alcohol in the presence of liquid hydrogen iluoride are given in the following table:

TABLE 1 Properties of reaction products from diacetone alcohol and polymer gasoline LOWER LAYER PRODUCT Bromne number 174 Maleic anhydride value 78 Mol. wt- 254 d42 0. 8658 Color (Gardner) 16 Viscosity (poises at 25 C.) below 5 m20.-- Spec. disp. Carbon, percent 86. 16 Hydrogen, percent 12. 00

DRYIN G TEST Without With dr1er drier D (dust free) days Below 1 3 Mlasx. Sward hardness 16 16 Dried hard, days 2 3 DISTILLATIONS-UPPER LAYER Wt. Perm1. gms. cent C.

6. 0 12. 7 Below 28 1.7 3.6 28- 50 5. 4 1l. 5 50-125 6. 9 14. 7 5. 8 12.3 9. 9 21. 0 11. 4 24. 2

LAYER 3. 0 7. 0 41-171 3. 8. 2 171-222 5. 6 13. 1 222-276 8. l 19. 0 276-325 22. 4 52. 7 above 325 EXANIPLE II Following the procedure used in Example I, 185 grams of the mentioned polymer gasoline, 52 grams of triacetin,

(CI-IaCOOCHzCH(OCOCI-I3) CHzOCOCI-Ia) and 193 grams of anhydrous hydrogen uoride 12 were stirred forV one hour at a temperature of 90-95 C. and at a maximum gage pressure of 98 pounds per square inch. The resultant liquid reaction mixture was then separated into 112 grams of upper layer and 313 grams of lower layer.

Conjunct polymerization occurred in this run, as evidenced by the fact that the upper layer consisted of substantially saturated hydrocarbons. The upper layer and pentane extract of the lower layer after washing with water and drying weighed 114 grams. The lower layer after hydrolysis and Water washing of the organic material yielded 74 grams of organic liquid. The carbon and hydrogen analysis of the lower layer product showed the presence of about 1.8% oxygen thus evidencing co-polymerization or condensation of the polymer gasoline and triacetin. About half of the drying oil material (lower layer product) boiled higher than 325 C. Drying tests on the entire lower layer product in the presence of drers showed that this material dried in 8 days to a non-brittle film with a Sward hardness of 15.

Further properties of the upper layer hydrocarbons and lower layer drying oil are given n Table 2.

TABLE 2 Properties of reaction products from triacetzn and polymer gasolme UPPER LAYER Bromine number 6 n.120 1.4248 Spec. disp- 102 d42'0-- 0.7599

LOWER LAYER PRODUCT Bromine number 190 Maleic anhydride value 72 .34221. Wt. 241 4 0. 8569 Color (Gardner) 16 Viscosity (poises at 25 C.) 0. 3 Carbon, percent 85. 76 Hydrogen, percentL 12. 40

DRYING TEST (WITH DRIER) Dust free in, days.. 5 Dried hard in, days 8 SWard hardness 15 DISTILLATIONS-UPPER LAYER Weight ml. gms. Percent C.

2. 5 6. 5 Below 28 13. 0 33. 9 28-225 6.0 15.6 225-275 4. 6 12. 0 275-325 12.3 32. 0 Above 325 LOWER LAYER 1. 7 5. 0 Below27 7. 7 22. 8 27-275 7. 6 22. 6 275-325 16. 7 49. 6 Above 325 being a saturated compound containing a radical. of the class consisting of aldehyde,Y ketone, can-- boxylic acid, ester and amide groups, agitating the reaction mixture for a time sufficient to form polymerization and condensation products and to effect hydrogen exchange to form a polyunsaturated drying oil and a saturated hydrocarbon material, separating the reaction mixture into a of one molar proportion of a carbonyl compound and from 1 to 50 molar proportions of propylene at a temperature of from about to about 175 C., said carbonyl compound being a saturated compound containing a radical of the class consisting of aldehyde, ketone, carboxylic acid, ester and amide groups, agitating the reaction mixture for a time suicient to form polymerization and condensation products and to eiect hydrogen exchange to form a polyunsaturated drying oil and a saturated hydrocarbon material, separating the reaction mixture into a hydrocarbon layer and a hydrouoric acid layer, recovering a drying oil from the hydroluoric acid layer, and recovering a saturated hydrocarbon product from the hydrocarbon layer.

3. A process for producing a drying oil which comprises mixing from about 0.1 to about parts by weight of hydrouoric acid of from about 90 to about 100% hydrogen fluoride concentration and one part by Weight of a mixture of one molar proportion of a carbonyl compound and from 1 to 50 molar proportions of butylene at a temperature of from about 0 to about 175 C., said carbonyl compound being a saturated compound containing a radical of the class consisting of aldehyde, ketone, carboxylic acid, ester and amide groups, agitating the reaction mixture for a time suiiicient to form polymerization and condensation products and to effect hydrogen exchange to form a polyunsaturated drying oil and a saturated hydrocarbon material, separating the reaction mixture into a hydrocarbon layer and a hydroluoric acid layer, recovering a drying oil from the hydrotluoric acid layer, and recovering a saturated hydrocarbon product from the hydrocarbon layer.

4. A process for producing a drying oil which comprises mixing from about 0.1 to about 10 parts by weight of hydrofluoric acid of from about to about 100% hydrogen uorde concentration and one part by Weight of a mixture of one molar proportion of a carbonyl compound and from 1 to 50 molar proportions of a normally liquid mono-olen at a temperature of from about 0 to about 175 C., said carbonyl compound being a saturated compound containing a radical of the class consisting of aldehyde, ketone, carboxylic acid, ester and amide groups, agitating the reaction mixture for a time sufcent to form polymerization and condensation products and to effect hydrogen exchange to form a polyunsaturated drying oil and a saturated hydrocarbon material, separating the reaction mixture into a hydrocarbon layer and a hydrofluoric acid layer, recovering a drying oil from the hydrouoric acid layer, and recovering a saturated hydrocarbon product from the hydrocarbon layer.

5. A process for producing a drying oil which comprises mixing from about 0.1 to about 10 parts by weight of hydrofluoric acid of from about 90 to about 100% hydrogen fluoride concentration and one part by weight of a mixture of one molar proportion of a carbonyl compound and from 1 to 50 molar proportions of polymer gasoline at a temperature of from about 0 to about C., said carbonyl compound being a saturated compound containing a radical of the class consisting of aldehyde, ketone, carboxylic acid, ester and amide groups, agitating the reaction mixture for a time sufficient to form polymerization and condensation products vand to effect hydrogen exchange to form a polyunsaturated drying oil and a saturated hydrocarbon material, separating the reaction mixture into a hydrocarbon layer and a hydrouo-ric acid layer, recovering a drying oil from the hydrofluoric acid layer, and recovering a saturated hydrocarbon product from the hydrocarbon layer.

HERMAN S. BLOCH. RICHARD C. WACKHER.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,252,333 Rothrock Aug. 12, 1941 2,253,323 Christman Aug. 19, 1941 2,400,521 Kuhn May 21, 1946 2,440,459 Bloch Apr, 27, 1948 2,440,477 Johnstone Apr. 27, 1948 

1. A PROCESS FOR PRODUCING A DRYING OIL WHICH COMPRISES MIXING FROM ABOUT 0.1 TO ABOUT 10 PARTS BY WEIGHT OF HYDROFLUORIC ACID OF FROM ABOUT 90 TO ABOUT 100% HYDROGEN FLUORIDE CONCENTRATION AND ONE PART BY WEIGHT OF A MIXTURE OF ONE MOLAR PROPORTION OF A CARBONYL COMPOUND AND FROM 1 TO 50 MOLAR PROPORTIONS OF A MONOOLEFINIC HYDROCARBON HAVING AT LEAST 3 CARBON ATOMS PER MOLECULE AT A TEMPERATURE OF FROM ABOUT 0* TO ABOUT 175* C., SAID CARBONYL COMPOUND BEING A SATURATED COMPOUND CONTAINING A RADICAL OF THE CLASS CONSISTING OF ALDEHYDE, KETONE, CARBOXYLIC ACID, ESTER AND AMINE GROUPS, AGITATING THE REACTION MIXTURE FOR A TIME SUFFICIENT TO FORM POLYMERIZATION AND CONDENSATION PRODUCTS, AND TO EFFECT HYDROGEN EXCHANGE TO FORM A POLYUNSATURATED DRYING OIL AND A SATURATED HYDROCARBON MATERIAL, SEPARATING THE REACTION MIXTURE INTO A HYDROCARBON LAYER AND A HYDROFLUORIC ACID LAYER, RECOVERING A DRYING OIL FROM THE HYDROFLUORIC ACID LAYER, AND RECOVERING A SATURATED HYDROCARBON PRODUCT FROM THE HYDROCARBON LAYER. 